Chemical Morphology of Frozen Mixed Nitrate-Salt Solutions

Surface chemistry on ice can play an important role in atmospheric composition, but uncertainties in the chemical partitioning within ice samples has hindered the development of accurate models of these systems. Using Raman microscopy, we examine the nitrate distribution in ice and liquid samples containing environmentally relevant concentrations of sodium chloride, sodium bromide, and sea salt analogue Instant Ocean. Nitrate is enhanced at the surface compared to in the bulk in all frozen samples but to different degrees depending on the added salt. A large variation of nitrate in the horizontal dimension of frozen samples provides direct evidence that it congregates in pockets or grain boundaries within the crystal. In these pockets, nitrate experiences a solution-like environment, whereas at the surface nitrate sometimes forms solid crystals.